Trisazo diphenyl dyestuffs



Patented Feb. 5.1946

UNITED STATES PATENT OFF-1C El TRISAZO: DIPHENYL DYESTUFFS Ai-tlfur Sieb'ert," mankrdrt-on-tfief-Main; er."- 'many, as'sig'nor toGeneralAniline &' Film" Cor-' por'ation; New 'Yorkg N. Y1; a corporationof Delaware N otDi'awing Application April-24.1941. Serial" No. 390,105.. In Germany May 15,-1940v Claims!- (Cl. 260 -17 2) The present invention relates to azo-dyestufis soluble in water; more particularly it relates/to dyestuffs of. the following-generar formula:

wherein R represents a radical of. the diphenyl series, the azo-groupsstanding in p-position to the diphenyl linkage, ande wherein the benzene nuclei R1, R2 and R3 may contain further substituents.

I have found that very valuable azo-dyestuffs capable of being metallized are obtained by con-- pling 1 mol of the tetrazocompound from*4.4-'- diaminodiphenyl or the thereof with 1 mol of.,1=hydroxybenzene-2-carboxylic acid or the nuclear substitution products thereof capable of being coupledand 1 mol of 1.3-dihydroxybenzene or the substitution prod ucts thereof capable of being coupled twice and combining-the dyestufi thus obtained with 1 mol of a diazo-compound containing a hydroxyl" group and a 'carboxyl group in ortho-position to each other.

The same dyestufis are obtained by combining 1 mol--ofa tetrazotized 4.4'-diaminodiphenyl" with. .-1 Im01 .0fi 1-hydroxybenzene-2-carboxylic acid. .or: the nuclear. substitution products .thereof capable of being coupled and l inol-of'a mono azo-dyestufis of the general constitution:

substitution productsafter-treatment" with g u dyestufi corresponds-with the followingxformulazinvention, but'a'th'ey are not intended to limit it thereto, the'parts being by weight, unless otherwise stated.

1. 18.4 parts" of 4.4'-diaminodiphenyl are suspended 500 parts by volume of water and parts by volume of crude hydrochloric acid and tetrazotize'd at 10 C. Theclear tetrazo solution is caused to run at 0 C. to 5 C.-into.-a-'solution of 15 parts of l-hydroxybenzene-Z-carboxy1ic acid in 300 parts by volume of 2N-sodium carbonate solution. As-soon asa tetrazo-compound can no longer -be detected, the--diazo-azo compound which has separated is combined with a solution, rendered alkalinev by means of sodium; carbonate, of 35. parts of the'monoazo-dyestufi;

obtained by coupling 'diazotized l-amino-2-hydroxybenzene-B-carboxylic acid-5-sulfonic acid with 1. 3="dihydroxybenzene, corresponding with the following formula:

M SOaH When the""coupling "is finished the trisazo' d'y stuif formed is precipitated with sodium chloride and isolated by filtration. When dry it is a dark brown powder which dissolves in water to "a brown solution and dyes cotton brown shades the fastness propertiesof which are improved'by'an' copoper' sulfate. The

2. If in Example 1 the 18.4 parts of 4.4-d1- aminodiphenyl are replaced by 24.4 parts of 4.4"- diamino-3.3-dimethoxydiphenyl, a redder brown shade-on cotton is obtained ties of which are considerably improved by an after-treatment with copper sulfate.

3. 24.4--parts of 4.4'-diamino-3.3'-dimethoxy diphenyl are suspended in 500 parts by volume of water and 50 parts by volume of crude hydrochloric acid. and tetrazotized at 10 C. The clear tetrazo solution is caused to run at 0 C. to 5 C. into a solution of 15 parts of l-hydroxybenzene-Z-carboxylic acid in 300 parts by volume of 2N-sodium carbonate solution. After about 15 hours a tetrazo-compound can at ordinary the fastness proper- 'erties:

Stuffv T e disazo-rdyestufi' is combined in a solution rendered alkaline. by means ofsodium carf A bonate or c ustic alkali, if necessary with addi-n tion of pyridine, with 23.3 grams of diazotized' l-amino-Z-hydroxy-benzene-fi-carboxylic acid-5- I l ic. c d 5 as mr i a -d tu 19 wherein R represents 'a'radical of the diphenyl ser'ies,= the az'o groups standingin p-position to the diph enyl linkage, being dark brown powders which dyes cotton red-brownssl'iades and'has properties very similar to thOse: of the dyestllfif; described in Example 2.

4. By' coupling 1 mol of .tetrazot'ized 4.4f-di- I am. e I V V V 1 The water-soluble azo-dyestuffs' o! the f01-' lowin eneral formula:

coon soon and yielding on-cotton dyeings which, when aftertreatedwith copper salts, change to brown shades amino-3.3-dimethyldiphenyl wan- "mol of 1; l5 of'very goodfastness to washing and to light.

I 'methyl-2-hydroxybenzene-3-carboxylic acid and combining the diazo-azo compound thus obtained f ing constitution:

' some a product is'obtained which is'very similar to the dyestuff described in Example 1,-

r no s lowing formula:

v X r n: 1 .i" g 1 H H V V j 003 it Y 1 00H 3 with mol of the monoazo-dyestufi of the follow- 25 being adark; brown powderwhich dissolves in water to a brown solution and dyes cotton brown 3 N: j shades whose fastness properties are improved by f I i v l 30 after-treatment with copper su1fate..f;v V H '11 -oo11 y v 3. The water-solubleanydyestuflor the followingformula: b K

V 'Q V The following table describes-a number of other axe-dyestuffs which may beobtained accordin to the present invention and have similar propbeingua dark brown powder which 'dis'solves'in' water to. a brown solution and dyes cotton red-; I dish brown shades-whose fastne'ss properties are improved by after-treatment with copper sulfate.

Constitution of the dyestufl- V ,treatedwithacop- Q 'parsaltf l-amino-Z-hydroxybenzene-3-carboxylic acid-5-si11ionic acid.

l-amino-2-hydroxybenzene3 carboxylic aoid-5-sulfonjc acid. l-hydroxybenzene-z-earboxylic acid 4.4-diammod1phenyl 1:11ydro iybenzene-acarboxylic acid v 4.4 -diamino-3.3-dichloro-diphenyl1 1.3-dlhydroxybenzene vReddish'bi'own;

l -amino-2-hydroxybenzene-3-ca1tboxyl1c acid-o-sulfonic acid. .7 e i .i I c q 1-hydroxybenzene-2-carboxylic acid 1-- -4.4-diammo-g-nitrodiphenyl 1.3-dihydroxybenzene 4' Yellowish brown.

l-hydroxybenzene-2-carboxylic acid 4. 4-diaminodiphenyi-B-SuIionic acid 1.3-dihydroxybenzene Beddish brown.

l-amino-2-hydroxybenzene-3-carboxyhc BQld-islllfqlilcjflld. n l-hydroxybenzene-2-carboxyhc sold 4-- 4.4'-d1aminodiphenyl- -g 1. 3-dihydroxy-2-methyib'enzene Brown.

I .7 1l3 -dihydroxybenzene-i-carboxyllc acid Reddish brown. l-amm -2-hydro xybenzene-ti-carboxylic'ac1d-5-sulfonlcacid.

4.Thewatersoluble azo-dyestufl of' the fol-' m. is o' semesters tawni as ailantsassass n 7 w to a wn spi ionand dy sfig mi red-1] dish brown shadeswhose fastness properties are improved by after-treatment with copper sulfate.

Shade .01 the dyeing 

